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The daughter of a nurse and a Royal Navy submariner, Pierson was born Emma Jane Pierson on 30 April 1981 in Plymouth, Devon. Her father, Charles, was stationed at Faslane Naval Base on the Clyde where Emma spent the first four years of her life.

After leaving Grange Hill, Pierson took on the role of Jackie Burgett in Days Like These, a British show set in Luton and adapted from the US comedy That '70s Show. However, Days Like These proved unsuccessful and the series was cancelled after only ten of its thirteen episodes were aired.

Pierson’s career has also included roles in comedy dramas such as Bedtime and Legend of the Tamworth Two. Also Emma in 2010 is starring in the Radio 4 comedy series "House on Fire".

Pierson has also appeared many dramas, including Stranded, the Hallmark channel's version of Swiss Family Robinson, BBC political drama The Project, Charles II and an as yet unreleased low-budget British movie, The Engagement, from the director of Sirens, John Duigan.

In 2005, Pierson played the role of policewoman Justine Hopkin in the two-part ITV drama, Bloodlines. She has since acted in many more dramas, such as Riot at the Rite, a period drama about Russian dancer Nijinsky, and Hotel Babylon, a BBC series based on the book of the same name by Imogen Edwards-Jones and portraying life behind the scenes in a London hotel.

British indie movie The Lives of the Saints, which was co-directed by Chris Cottam and photographer Rankin and in which Emma played a character called Tina, was released in 2006. This was Pierson’s first major movie role, after brief roles in Virtual Sexuality and Guest House Paradiso early in her career.